The actress and fashion model will be joining Scarlett Johansson as the face of the Italian brand.
The stunning actress will launch her own limited-edition range lipstick with the brand.
The desing duo and Monica are not on their first collaboration as she has also posed for their Spring 2012 campaign for the brand’s ready-to-wear collection.
Domenico Dolce said: “We love Monica and have worked with her many times over the past 20 years. Her beauty is timeless. She expresses the Dolce & Gabbana woman perfectly,”
Domenico’s partner, Stefano Gabbana, added: “She is ravishing – a true Italian icon.”
The 47-year-old beauty said: “I’m delighted to be collaborating with Domenico and Stefano on Dolce & Gabbana The Make Up. I have always adored the aesthetic of Dolce & Gabbana and it’s so exciting to be involved with their creative process.”